TW201920368A - Polyimide, polyimide varnish, and polyimide film - Google Patents

Abstract

The present invention provides a polyimide in which a structural unit A derived from a tetracarboxylic acid or a derivative thereof includes a structural unit (A-1) derived from a compound (a-1), a structural unit B derived from a diamine includes a structural unit (B-1) derived from a compound (b-1), a structural unit (B-2) derived from a compound (b-2), and at least one structural unit selected from among structural units (B-3) to (B-5) derived from compounds (b-3) to (b-5) respectively, wherein relative to the structural unit B, the proportion of the structural unit (B-1) is less than 50 mol%, the proportion of the structural unit (B-2) is at least 15 mol%, and the proportion accounted for by the combination of the structural unit (B-1) and the structural unit (B-2) is at least 50 mol%, as well as providing a polyimide film containing the above polyimide, a polyimide that can form a film having low retardation and excellent elongation, and a polyimide varnish and polyimide film that contain the polyimide.

Description

Polyimide, polyimide varnish, and polyimide film

The present invention relates to polyimide, and polyimide varnish and polyimide film containing the polyimide.

Polyimide has excellent heat resistance, and has excellent properties in mechanical properties, chemical resistance, electrical properties, etc., so it is used in molding materials, composite materials, electrical-electronic parts, optical materials, displays, aerospace and other fields Among them, polyimide films are widely used as materials.
Some people have discussed the use of plastic films instead of glass substrates in optical devices such as liquid crystal displays (LCDs), in order to achieve weight reduction, thinness, and flexibility, and hope that the characteristics required for plastic films, that is, phase The difference is small and the phase delay is low.

For a plastic film material that can meet the requirements as described above, for example, Patent Document 1 discloses the use of 1,2,4,5-cyclohexanetetracarboxylic dianhydride as the tetracarboxylic acid component and the use of 9,9- Poly (imino) imide synthesized from bis (3-methyl-4-aminophenyl) fluorene and 4,4'-diaminodiphenyl ether as diamine components.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent No. 6010533

[Problems to be Solved by the Invention]

However, although the polyimide disclosed in Patent Document 1 is excellent in transparency and heat resistance and has a small phase difference, the elongation of one of the indicators of strength and toughness has not reached a satisfactory level. In order to achieve the thinness of the plastic film And flexible, further improvement is necessary.
That is, the problem to be solved by the present invention is to provide a polyimide which can form a film with low phase retardation and excellent extensibility, and a polyimide varnish and a polyimide film including the polyimide.
[Means for solving problems]

As a result of intensive investigations by the present inventors, it has been found that polyimide composed of specific constituent units can form a thin film with low phase retardation and excellent extensibility. Based on these findings, the present invention has been completed. That is, the present invention relates to the following [1] to [3].
[1] A polyimide having a constitutional unit A derived from a tetracarboxylic acid or a derivative thereof and a constitutional unit B derived from a diamine,
The structural unit A includes a structural unit (A-1) derived from a compound represented by the following formula (a-1),
The structural unit B includes a structural unit (B-1) derived from a compound represented by the following formula (b-1), a structural unit (B-2) derived from a compound represented by the following formula (b-2), and a component selected from the group consisting of The constituent unit (B-3) of the compound represented by the formula (b-3), the constituent unit (B-4) derived from the compound represented by the following formula (b-4), and the compound represented by the following formula (b-5) At least one of the constituent units (B-5),
The proportion of the constituent unit (B-1) to the constituent unit B is less than 50 mol%, and the proportion of the constituent unit (B-2) to the constituent unit B is 15 mol% or more. The constituent units (B-1) and The proportion of the total of the constituent units (B-2) in the constituent unit B is 40 mol% or more.

[Chemical 1]

[Chemical 2]

In formula (b-1), R each independently represents a hydrogen atom, a fluorine atom, or a methyl group.

[2] A polyimide varnish obtained by dissolving the polyimide according to [1] in an organic solvent.
[3] A polyimide film containing the polyimide according to [1].
[Effect of the invention]

According to the present invention, a polyimide capable of forming a film with low phase retardation and excellent extensibility, and a polyimide varnish and a polyimide film containing the polyimide can be provided.

The polyfluorene imide of the present invention has a constitutional unit A derived from a tetracarboxylic acid or a derivative thereof and a constitutional unit B derived from a diamine,
The structural unit A includes a structural unit (A-1) derived from a compound represented by the above formula (a-1),
The structural unit B includes a structural unit (B-1) derived from the compound represented by the above formula (b-1), a structural unit (B-2) derived from the compound represented by the above formula (b-2), and a component selected from the above The constituent unit (B-3) of the compound represented by the formula (b-3), the constituent unit (B-4) derived from the compound represented by the above formula (b-4), and the compound represented by the aforementioned formula (b-5) At least one of the constituent units (B-5),
The proportion of the constituent unit (B-1) to the constituent unit B is less than 50 mol%, and the proportion of the constituent unit (B-2) to the constituent unit B is 15 mol% or more. The constituent units (B-1) and The proportion of the total of the constituent units (B-2) in the constituent unit B is 40 mol% or more.
The polyimide of the present invention will be described below.

[Construction unit A]
The structural unit A contained in the polyfluorene imide of the present invention is a structural unit derived from a tetracarboxylic acid or a derivative thereof. The tetracarboxylic acid or a derivative thereof may be used alone or in combination of two or more kinds.
Examples of the derivative of tetracarboxylic acid include anhydrides or alkyl esters of tetracarboxylic acid. The alkyl ester of a tetracarboxylic acid preferably has a carbon number of 1 to 3, and examples thereof include dimethyl esters, diethyl esters, and dipropyl esters of tetracarboxylic acids. In the case of tetracarboxylic acid or a derivative thereof, tetracarboxylic dianhydride is preferable.
The constitutional unit A in the present invention includes a constitutional unit (A-1) derived from a compound represented by the following formula (a-1). The compound represented by formula (a-1) is 1,2,4,5-cyclohexanetetracarboxylic dianhydride. When the constitutional unit A includes the constitutional unit (A-1), the transparency and heat resistance of the polyimide are improved.

[Chemical 3]

The proportion of the constituent unit (A-1) to the constituent unit A should preferably be 70 to 100 mol%, more preferably 85 to 100 mol%, even more preferably 99 to 100 mol%, and even more preferably 100 mol%. Better.

As long as the polyimide of the present invention does not impair the effect of the present invention, the constitutional unit A may include a constitutional unit derived from a tetracarboxylic dianhydride other than the compound represented by the formula (a-1) as the aforementioned constitution. It is preferable that the structural unit other than the unit (A-1) is not included.

[Construction unit B]
The structural unit B contained in the polyfluorene imide of the present invention is a structural unit derived from a diamine.
The aforementioned constitutional unit B includes a constitutional unit (B-1) derived from a compound represented by the following formula (b-1).

[Chemical 4]

In the formula (b-1), R is independently selected from the group consisting of a hydrogen atom, a fluorine atom, and a methyl group, and is preferably a hydrogen atom.
Examples of the compound represented by the above formula (b-1) include 9,9-bis (4-aminophenyl) fluorene and 9,9-bis (3-fluoro-4-aminophenyl) fluorene. And 9,9-bis (3-methyl-4-aminophenyl) fluorene, etc., is preferably at least one selected from the group consisting of these three compounds and is 9,9-bis ( 4-Aminophenyl) fluorene is more preferred.
By including the aforementioned constitutional unit (B-1), the polyimide of the present invention can reduce the phase difference and exhibit a low phase delay.
In the present invention, the ratio of the constituent unit (B-1) to the constituent unit B is less than 50 mol%. When the ratio of the said structural unit (B-1) is 50 mol% or more, it will become difficult to form the film excellent in extensibility. Considering the viewpoint of exhibiting a low phase retardation and forming a film with excellent stretchability, the proportion of the aforementioned constituent unit (B-1) should be 45 mol% or less, more preferably 42 mol% or less, and more preferably 40 mol% or less 5 mol% or more, more preferably 10 mol% or more, more preferably 15 mol% or more, and more preferably 20 mol% or more. Considering the same viewpoint as the foregoing, the proportion of the aforementioned constituent unit (B-1) should be 5 to 45 mol%, more preferably 10 to 45 mol%, more preferably 15 to 45 mol%, and even more preferably 20 to 40 mol% is even better.

The structural unit B in the present invention includes a structural unit (B-2) derived from a compound represented by the following formula (b-2).

[Chemical 5]

The compound represented by the formula (b-2) is 2,2-bis [4- (4-aminophenoxy) phenyl] propane.
The polyfluorene imide of the present invention can reduce the phase difference and form a thin film having excellent low phase retardation and excellent extensibility by including the aforementioned constitutional unit (B-2).
In this invention, the ratio of the said structural unit (B-2) with respect to the structural unit B is 15 mol% or more. If the ratio of the aforementioned structural unit (B-2) is less than 15 mol%, it becomes difficult to form a thin film with low phase retardation and excellent extensibility. Considering the viewpoint of forming a thin film with low phase retardation and excellent extensibility, the proportion of the aforementioned constituent unit (B-2) should be 20 mol% or more, more preferably 25 mol% or more, and more preferably 30 mol% or more. It is more than 35 mol% and more preferably, more than 40 mol% and more preferably, and preferably 70 mol% or less, more preferably 60 mol% or less, and more preferably 50 mol% or less. Considering the same viewpoint as the foregoing, the proportion of the aforementioned constituent unit (B-2) should preferably be 15 to 70 mol%, more preferably 15 to 60 mol%, more preferably 20 to 50 mol% and even more preferably 30 to 50 mol% is even better, 35 to 50 mol% is even better, and 40 to 50 mol% is even better.

In the present invention, the proportion of the total of the constituent units (B-1) and (B-2) in the constituent unit B is 40 mol% or more. If the ratio of the total of the above-mentioned constituent units (B-1) and (B-2) is less than 40 mol%, it becomes difficult to form a thin film with low phase retardation and excellent extensibility. The proportion of the total of the aforementioned constituent units (B-1) and (B-2) is preferably 50 mol% or more, more preferably 55 mol% or more, more preferably 60 mol% or more, and more preferably 95 mol% or less, more preferably 90 mol% or less. Considering the same viewpoint as above, the proportion of the total of the above-mentioned constituent units (B-1) and (B-2) should be 40 to 95 mole%, more preferably 50 to 95 mole%, and 55 to 95. Morse% is even better, 60 ~ 90 Morse% is even better.

The structural unit B in the present invention includes a structural unit (B-3) selected from a compound represented by the following formula (b-3), a structural unit (B-4) derived from the following formula (b-4), and At least one type of constituent unit from the group consisting of constituent units (B-5) of the compound represented by the following formula (b-5) (hereinafter, this constituent unit may be referred to as "constituent unit B '"). When the constitutional unit B includes the constitutional unit B ', a thin film having excellent balance between low phase retardation and extensibility can be obtained.

[Chemical 6]

The compound represented by the above formula (b-3) is 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane. The compound represented by the above formula (b-4) is 5-amino-1,3,3-trimethyl-1- (4-aminophenyl) dihydroindane. The compound represented by the above formula (b-5) is 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl (alias: 2,2'-bis (trifluoromethyl) biphenyl aniline).
The constitutional unit B ′ may include all of the constitutional units (B-3) to (B-5), but may be selected from the constitutional unit (B-3), the constitutional unit (B-4), and the constitution. One or two constituent units in the group of unit (B-5) are preferable, and one constituent unit is more preferable.

The proportion of the total of the aforementioned constitutional unit (B-3), constitutional unit (B-4), and constitutional unit (B-5) in constitutional unit B is preferably 5 to 60 mole%, and is 10 to 50 Molar% is more preferred, 10 to 45 mole% is even better, and 10 to 40 mole% is even better.
When the aforementioned constitutional unit (B-3) is included as the constitutional unit B ', the proportion of the constitutional unit (B-3) to the constitutional unit B is preferably 10 to 60 mol%, more preferably 25 to 55 mol%, It is more preferably 35 to 50 mol%, and even more preferably 40 to 50 mol%.
When the aforementioned constitutional unit (B-4) is included as the constitutional unit B ', the proportion of the constitutional unit (B-4) to the constitutional unit B is preferably 10 to 60 mole%, and more preferably 20 to 55 mole%. It is even more preferably 30 to 50 mol%, and even more preferably 35 to 50 mol%.
When the aforementioned constitutional unit (B-5) is included as the constitutional unit B ', the proportion of the constitutional unit (B-5) to the constitutional unit B is preferably 5 to 40 mole%, and more preferably 5 to 30 mole%. 5 to 20 mol% is even better, and 5 to 15 mol% is even better.

The polyfluorene imide of the present invention may include a constituent unit derived from a diamine other than the compound represented by the formulae (b-1) to (b-5) in the range in which the effect of the present invention is not impaired. , But not ideal.
The proportion of constituent units derived from diamines other than the compounds represented by the above formulae (b-1) to (b-5) to constituent unit B is preferably 10 mol% or less, more preferably 5 mol% or less, and is 1 Molar% is more preferred, and 0 Molar% is even better.

[Manufacturing method of polyimide]
The polyfluorene imide of the present invention is obtained by reacting a diamine component and a tetracarboxylic acid component.

Examples of the tetracarboxylic acid component include tetracarboxylic acid or a derivative thereof. The tetracarboxylic acid component can be used alone or in combination of two or more.
Examples of the derivative of a tetracarboxylic acid include anhydrides or alkyl esters of the tetracarboxylic acid.
The alkyl ester of a tetracarboxylic acid preferably has a carbon number of 1 to 3, and examples thereof include dimethyl esters, diethyl esters, and dipropyl esters of tetracarboxylic acids.
Among the tetracarboxylic acid components used in the present invention, 1,2,4,5-cyclohexanetetracarboxylic acid or a derivative thereof is necessary, and it is preferable to include 1,2,4,5-cyclohexanetetracarboxylic acid. Dianhydride [Formula (a-1) above].

The amount of 1,2,4,5-cyclohexanetetracarboxylic acid or its derivative is preferably 70 to 100 mole%, more preferably 85 to 100 mole%, relative to all the tetracarboxylic acid components, and is 99. ~ 100 mole% is even better, and 100 mole% is even better.

In addition, it may contain a tetracarboxylic acid component other than 1,2,4,5-cyclohexanetetracarboxylic acid or a derivative thereof. The tetracarboxylic acid component may be at least one selected from the group consisting of a tetracarboxylic acid or a derivative containing an aromatic ring and a tetracarboxylic acid or a derivative containing an alicyclic hydrocarbon structure. Species. This tetracarboxylic acid component can be used individually or in combination of 2 or more types.
Examples of tetracarboxylic acids containing aromatic rings include pyromellitic acid, 3,3 ', 4,4'-diphenylarsinetetracarboxylic acid, 3,3', 4,4'-benzophenone Tetracarboxylic acid, 4,4'-oxydiphthalic acid, 4,4 '-(hexafluoroisopropylidene) diphthalic acid, 2,2', 3,3'-benzophenone tetra Carboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 2,2 ', 3,3'-biphenyltetracarboxylic acid , 2,2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (2,3-dicarboxyphenyl) propane, 2,2-bis (3,4-dicarboxyphenoxy) Phenyl) propane, 1,1-bis (2,3-dicarboxyphenyl) ethane, 1,2-bis (2,3-dicarboxyphenyl) ethane, 1,1-bis (3,4 -Dicarboxyphenyl) ethane, 1,2-bis (3,4-dicarboxyphenyl) ethane, bis (2,3-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) ) Methane, 4,4 '-(p-phenylenedioxy) diphthalic acid, 4,4'-(m-phenylenedioxy) diphthalic acid, 2,3,6,7 -Naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid and their derivatives.

As for the tetracarboxylic acid containing an alicyclic hydrocarbon structure, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,4,5-cyclopentanetetracarboxylic acid, bicyclic [2.2 .2] oct-7-ene-2,3,5,6-tetracarboxylic acid, dicyclohexyltetracarboxylic acid, cyclopentanone dispiro norbornane tetracarboxylic acid or their positional isomers, and their derivative.
Examples of the tetracarboxylic acid component having no alicyclic hydrocarbon structure and no aromatic ring include 1,2,3,4-butanetetracarboxylic acid and 1,2,3,4-pentanetetracarboxylic acid. Acids, etc. or their derivatives.

The amount of tetracarboxylic acid components other than 1,2,4,5-cyclohexanetetracarboxylic acid or its derivative is preferably 30 mol% or less, and 15 mol% or less with respect to all the tetracarboxylic acid components. It is preferably 1 mol% or less and more preferably, and 0 mol% or more.

The diamine component used in the present invention is not limited to the diamine providing the constituent unit B, and may be a diisocyanate corresponding to the diamine, but a diamine is preferred.
The diamine component used in the present invention includes a compound represented by the above formula (b-1) and a compound represented by the above formula (b-2), and further includes a compound selected from the above formula (b-3) and the above formula The compound represented by (b-4) and at least one compound among the compounds represented by said Formula (b-5) are preferable.
In addition, 5-amino-1,3,3-trimethyl-1- (4-aminophenyl) dihydroindene (hereinafter sometimes referred to as "5-amino group" Isomers ") may be mixed with 6-amino-1,3,3-trimethyl-1- (4-aminophenyl) dihydroindane (hereinafter sometimes referred to as" 6-amino isomers "). That is, when the compound represented by the formula (b-4) is used as the diamine component, the 5-amino isomer and the 6-amino isomer may be mixed together in some cases.

The amount of the compound represented by the above formula (b-1) is less than 50 mol%, preferably 5 to 45 mol%, more preferably 10 to 45 mol%, and more preferably 15 to 45, relative to the total diamine component. Molar% is even better, 20 to 40 Molar% is even better.
The amount of the compound represented by the above formula (b-2) is 15 mol% or more, preferably 15 to 70 mol%, more preferably 15 to 60 mol%, and more preferably 20 to 50, relative to all the diamine components. Molar% is even better, 30-50 Molar% is even better, 35-50 Molar% is even better, and 40-50 Molar% is even better.
The total amount of the compound represented by the formula (b-1) and the compound represented by the formula (b-2) is 40 mol% or more, preferably 40 to 95 mol%, relative to all the diamine components, which is 50 ~ 95 mole% is better, 55 ~ 95 mole% is even better, and 60 ~ 90 mole% is even better.
The total amount of the compound represented by the formula (b-3), the compound represented by the formula (b-4), and the compound represented by the formula (b-5) is preferably 5 to 60 moles relative to all the diamine components. Ear% is more preferably 10 to 55 mole%, more preferably 10 to 50 mole%, and even more preferably 10 to 45 mole% and more preferably 10 to 40 mole% and more preferably.
The amount of the compound represented by the above formula (b-3) is preferably 10 to 60 mol%, more preferably 25 to 55 mol%, and more preferably 35 to 50 mol%, relative to all the diamine components. It is more preferably 40 to 50 mol%.
The amount of the compound represented by the above formula (b-4) is preferably 10 to 60 mol%, more preferably 20 to 55 mol%, and more preferably 30 to 50 mol%, relative to all the diamine components. It is more preferably 35 to 50 mol%.
The amount of the compound represented by the above formula (b-5) should be 5 to 40 mole%, more preferably 5 to 30 mole%, and even more preferably 5 to 20 mole%, relative to all the diamine components. It is more preferably 5 to 15 mol%.

The diamine component may include diamine components other than the compounds represented by the above formulae (b-1) to (b-5). The diamine component includes at least one selected from the group consisting of an aromatic diamine and an aliphatic diamine. This diamine component can be used individually or in combination of 2 or more types. In addition, "aromatic diamine" refers to a diamine in which an amine group is directly bonded to an aromatic ring, and a part of its structure may include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and other substituents (for example, a halogen atom, a sulfonic acid, or the like). Fluorenyl, carbonyl, oxygen, etc.). "Aliphatic diamine" means a diamine in which an amine group is directly bonded to an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, and a part of its structure may also include an aromatic hydrocarbon group and other substituents (for example, a halogen atom, a sulfonyl group , Carbonyl, oxygen atom, etc.).

Examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, benzidine, o-tolylamine, and m-phenylene Toluidine, octafluorobenzidine, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3, 3'-dichloro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,6-diaminonaphthalene, 1,5-di Amino naphthalene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Hydrazone, 3,4'-diaminodiphenylhydrazone, 4,4'-diaminobenzophenone, 2,2-bis [4- (2-methyl-4-aminophenoxy) benzene Yl] propane, 2,2-bis [4- (2,6-dimethyl-4-aminophenoxy) phenyl] propane, 2,2-bis [4- (2-methyl-4- Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2,6-dimethyl-4-aminophenoxy) phenyl] hexafluoropropane, 4,4'- Bis (4-aminophenoxy) biphenyl, 4,4'-bis (2-methyl-4-aminophenoxy) biphenyl, 4,4'-bis (2,6-dimethyl -4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) Phenyl] fluorene, bis [4- (2-methyl-4-aminophenoxy) phenyl] fluorene, bis [4- (2,6-dimethyl-4-aminophenoxy) benzene Yl] fluorene, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (2-methyl-4-aminophenoxy) phenyl] ether, bis [4- ( 2,6-dimethyl-4-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (2-methyl-4- Aminophenoxy) benzene, 1,4-bis (2,6-dimethyl-4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1, 3-bis (2-methyl-4-aminophenoxy) benzene, 1,3-bis (2,6-dimethyl-4-aminophenoxy) benzene, 1,4-bis (4 -Amino-α, α-dimethylbenzyl) benzene, 2,2-bis (4-aminophenyl) propane, 2,2-bis (2-methyl-4-aminophenyl) propane , 2,2-bis (3-methyl-4-aminophenyl) propane, 2,2-bis (3-ethyl-4-aminophenyl) propane, 2,2-bis (3,5 -Dimethyl-4-aminophenyl) propane, 2,2-bis (2,6-dimethyl-4-aminophenyl) propane, 2,2-bis (4-aminophenyl) Hexafluoropropane, 2,2-bis (2-methyl-4-aminophenyl) hexafluoropropane, 2,2-bis (2,6-dimethyl-4-aminophenyl) hexafluoropropane Α, α'-bis (4-aminophenyl) -1,4-diisopropylbenzene, α, α'-bis (2-methyl-4-aminophenyl) Group) -1,4-diisopropylbenzene, α, α'-bis (2,6-dimethyl-4-aminophenyl) -1,4-diisopropylbenzene, α, α ' -Bis (3-aminophenyl) -1,4-diisopropylbenzene, α, α'-bis (4-aminophenyl) -1,3-diisopropylbenzene, α, α ' -Bis (2-methyl-4-aminophenyl) -1,3-diisopropylbenzene, α, α'-bis (2,6-dimethyl-4-aminophenyl) -1 , 3-diisopropylbenzene, α, α'-bis (3-aminophenyl) -1,3-diisopropylbenzene, 9,9-bis (2-methyl-4-aminophenylbenzene Yl) fluorene, 9,9-bis (2,6-dimethyl-4-aminophenyl) fluorene, 1,1-bis (4-aminophenyl) cyclopentane, 1,1-bis ( 2-methyl-4-aminophenyl) cyclopentane, 1,1-bis (2,6-dimethyl-4-aminophenyl) cyclopentane, 1,1-bis (4-amine Phenyl) cyclohexane, 1,1-bis (2-methyl-4-aminophenyl) cyclohexane, 1,1-bis (2,6-dimethyl-4-aminophenyl) ) Cyclohexane, 1,1-bis (4-aminophenyl) -4-methyl-cyclohexane, 1,1-bis (4-aminophenyl) norbornane, 1,1-bis (2-methyl-4-aminophenyl) norbornane, 1,1-bis (2,6-dimethyl-4-aminophenyl) norbornane, 1,1-bis (4- Aminophenyl) adamantane, 1,1-bis (2-methyl-4-aminophenyl) adamantane, 1,1-bis (2,6-dimethyl-4-aminophenyl) gold Dioxane and the like.

They can be used alone or in combination of two or more.

Examples of the aliphatic diamine include ethylene diamine, hexamethylene diamine, polyethylene glycol bis (3-aminopropyl) ether, and polypropylene glycol bis (3-aminopropyl) ether. , 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, m-xylylenediamine, p-xylylenediamine, 1,4-bis (2 -Amine-isopropyl) benzene, 1,3-bis (2-amino-isopropyl) benzene, isophoronediamine, norbornanediamine, siloxanediamine, 4,4 ' -Diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminobicyclo Hexylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane, 2,3-bis (aminomethyl) -bicyclo [2.2.1] heptane , 2,5-bis (aminomethyl) -bicyclo [2.2.1] heptane, 2,6-bis (aminomethyl) -bicyclo [2.2.1] heptane, 2,2-bis (4 , 4'-diaminocyclohexyl) propane, 2,2-bis (4,4'-diaminomethylcyclohexyl) propane and the like.

The amount of the diamine component other than the compounds represented by the formulae (b-1) to (b-5) is preferably 10 mol% or less, more preferably 5 mol% or less, and is 1 with respect to all the diamine components. Molar% is more preferred, and 0 Molar% is even better.

When manufacturing the polyfluorene imide of the present invention, in terms of the feed amount ratio of the tetracarboxylic acid component to the diamine component, the diamine component is preferably 0.9 to 1.1 mole relative to 1 mole of the tetracarboxylic acid component.

In the production of the polyfluorene imide of the present invention, the aforementioned tetracarboxylic acid component and the aforementioned diamine component are used, and in addition, a blocking agent may be used. As for the capping agent, it is preferably a monoamine or a dicarboxylic acid. Relative to 1 mole of the tetracarboxylic acid component, the feeding amount of the capping agent added should preferably be 0.0001 to 0.1 mole, more preferably 0.001 to 0.06 mole. For monoamine-based capping agents, it is recommended to use, for example: methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine , 3-methylbenzylamine, 3-ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline and the like. Among them, benzylamine and aniline can be preferably used. As for the dicarboxylic acid-type end-capping agent, it is preferably a dicarboxylic acid, and a part thereof may be ring-closed. Suggestions are, for example: phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenone dicarboxylic acid, 3,4-benzophenone Dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, and the like. Among them, phthalic acid and phthalic anhydride can be preferably used.

The method of reacting the tetracarboxylic acid component and the diamine component is not particularly limited, and a known method can be used.
Specific reaction methods include: (1) feeding a tetracarboxylic acid component, a diamine component, and a reaction solvent to a reactor, stirring at room temperature to 80 ° C for 0.5 to 30 hours, and then heating up to implement方法 The method of imidization reaction; (2) Feed the diamine component and the reaction solvent into the reactor and dissolve them, and then feed the tetracarboxylic acid component. Stir 0.5 ~ 30 at room temperature ~ 80 ℃ if necessary Hours, then raise the temperature to carry out the method of hydrazone imidization reaction; (3) feed the tetracarboxylic acid component, diamine component, and reaction solvent to the reactor, and immediately raise the temperature to implement the method of hydrazone imidization reaction, etc. .

The reaction solvent used for the production of polyfluorene imine may be any one that does not interfere with the fluorene imidization reaction and can dissolve the polyfluorene formed. Examples thereof include aprotic solvents, phenol-based solvents, ether-based solvents, and carbonate-based solvents.

Specific examples of the aprotic solvent include N, N-dimethylisobutyramide, N, N-dimethylformamide, N, N-dimethylacetamide, and N- Methylamine-based solvents such as methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethylimidazolidone, and tetramethylurea; γ-butyrolactone, γ-valerolactone Isolactone-based solvents; phosphonium-based amines such as hexamethylphosphamide and hexamethylphosphinetriamine; sulfur-based solvents such as dimethyl hydrazone, dimethylmethane, and cyclobutane; acetone , Ketone solvents such as cyclohexanone and methylcyclohexanone; amine solvents such as methylpyridine and pyridine; ester solvents such as 2-methoxy-1-methylethyl acetate.

Specific examples of the phenol-based solvent include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, and 2,5-diphenol. Methylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, etc.
Specific examples of the ether-based solvent include 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, and 1,2-bis (2-methoxyethoxy). ) Ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,4-dioxane and the like.
Specific examples of the carbonate-based solvent include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, and propylene carbonate.
Among the above-mentioned reaction solvents, an aprotic solvent is preferred, a fluorene-based solvent or a lactone-based solvent is more preferred, and γ-butyrolactone is even more preferred. Moreover, the said reaction solvent can be used individually or in mixture of 2 or more types.

It is preferred to use a Dean-Stark device for the hydrazone imidization reaction, and to perform the reaction while removing the water generated during production. By carrying out such an operation, the polymerization degree and the fluorenimide ratio can be further increased.

A known fluorene imidization catalyst can be used in the fluorene imidization reaction. Examples of the sulfonium imidization catalyst include an alkali catalyst and an acid catalyst.
Examples of the base catalyst include pyridine, quinoline, isoquinoline, α-methylpyridine, β-methylpyridine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, and trimethyl Organic base catalysts such as amine, triethylamine, tripropylamine, tributylamine, imidazole, N, N-dimethylaniline, N, N-diethylaniline; potassium hydroxide, sodium hydroxide, potassium carbonate, carbonic acid Catalysts for inorganic bases such as sodium, potassium bicarbonate and sodium bicarbonate.
Examples of the acid catalyst include crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, hydroxybenzoic acid, terephthalic acid, benzenesulfonic acid, P-toluenesulfonic acid, naphthalenesulfonic acid, etc. The said sulfonium imidization catalyst can be used individually or in combination of 2 or more types.
Among the above, in view of operability, an alkali catalyst is preferred, an organic alkali catalyst is more preferred, and triethylamine is even more preferred.

When the catalyst is used, the reaction temperature and the viewpoint of inhibiting gelation are considered. The temperature of the imidization reaction is preferably 120 to 250 ° C, more preferably 160 to 190 ° C, and even more preferably 180 to 190 ° C. The reaction time is preferably 0.5 to 10 hours after the start of the distillation of the produced water.
In addition, the temperature of the amidation reaction of the amidine when no catalyst is used is preferably 200 to 350 ° C.

[Polyimide]
In consideration of the mechanical strength of the obtained polyimide film, the weight average molecular weight of the polyimide of the present invention is preferably 500 to 1,000,000. The weight average molecular weight of polyimide can be measured by gel filtration chromatography or the like.
Examples of the measurement of the weight average molecular weight include a method of measuring the absolute molecular weight by using a light scattering detector using N, N-dimethylformamide as a developing solvent.

The polyimide of the present invention may be further mixed with various additives as long as the effect of the present invention is not impaired. Examples of the additives include antioxidants, light stabilizers, surfactants, flame retardants, plasticizers, inorganic fillers, and polymer compounds other than the aforementioned polyimide.
Examples of the polymer compound include polyimide, polycarbonate, polystyrene, polyimide, polyimide, and polyethylene terephthalate other than the polyimide of the present invention. Such as polyester, polyether fluorene, polycarboxylic acid, polyacetal, polyphenylene ether, polyfluorene, polybutene, polypropylene, polypropylene amine, polyvinyl chloride and so on.

[Polyimide varnish]
The polyimide varnish of the present invention is obtained by dissolving the polyimide of the present invention in an organic solvent. That is, the polyimide varnish of the present invention is a solution containing the polyimide of the present invention, which contains the polyimide of the present invention and an organic solvent, and the polyimide is dissolved in the organic solvent.
The organic solvent is not particularly limited as long as it can dissolve polyimide, and it is preferable to use the above-mentioned compounds exemplified as a reaction solvent used in the production of polyimide, alone or in combination of two or more.
The polyimide of the present invention has solvent solubility, so it can be made into a stable high concentration varnish at room temperature.

The polyimide varnish may be a polyimide-containing solution itself in which the polyimide obtained by the polymerization method is dissolved in a reaction solvent. It is also possible to mix at least one selected from the solvents exemplified above as a solvent for dissolving polyimide in the polyimide-containing solution.

The solid content concentration of the solution containing the polyimide of the present invention (the polyimide varnish of the present invention) can be appropriately selected depending on the workability and the like when forming a polyimide film described later, and the polymer of the present invention can be produced. The reaction solvent used in the sulfonium imine volatilizes and concentrates, or adjusts the solid content concentration and viscosity by adding an organic solvent. The organic solvent is not particularly limited as long as it can dissolve the polyfluorene imine of the present invention.
The solid content concentration of the solution containing the polyimide of the present invention (polyimide varnish of the present invention) is preferably 5 to 60% by mass, and more preferably 10 to 45% by mass. The solution viscosity of the polyimide of the present invention is preferably 1 to 200 Pa200s, and more preferably 5 to 150 Pa ･ s.
The solution viscosity of polyimide is a value measured at 23 ° C using an E-type viscometer.

[Polyimide film]
The polyimide film of the present invention contains the polyimide of the present invention and is characterized by low phase retardation and excellent extensibility. The polyimide film of the present invention is preferably composed of the polyimide of the present invention.
The method for producing the polyimide film of the present invention is not particularly limited, and a known method can be used. Examples include coating a glass plate with a solution containing the polyimide of the present invention (the polyimide varnish of the present invention), or a solution containing the polyimide of the present invention and the various additives described above, A method for removing solvent components such as organic solvents contained in the solution on a smooth support such as a metal plate or plastic or after forming a thin film.

The polyimide-containing solution may be a polyimide solution itself obtained by dissolving a polyimide obtained by a polymerization method in a reaction solvent. Moreover, it can also be made by mixing at least 1 sort (s) chosen from the said solvent exemplified as the solvent which melt | dissolves the polyfluorene imide in the said polyfluorene imine solution. By adjusting the solid content concentration and viscosity of the solution containing polyimide as described above, the thickness of the polyimide film of the present invention can be easily controlled.

The surface of the said support body may apply a mold release agent as needed. The method of applying the solution containing the said polyfluorene imine to the said support body, and heating and evaporating a solvent component is preferable as follows. That is, it is preferable to evaporate the solvent at a temperature of 120 ° C or lower to prepare a self-supporting film, then peel the self-supporting film from the support, and then fix the end of the self-supporting film to the The solvent component is dried at a temperature higher than the boiling point of 350 ° C to produce a polyimide film. In addition, it is preferable to perform drying under a nitrogen environment. The pressure of the dry ambient gas may be reduced pressure, normal pressure, or pressurized.

The thickness of the polyfluorene imide film of the present invention can be appropriately selected according to the application and the like, but it is preferably from 1 to 250 μm, more preferably from 5 to 100 μm, and even more preferably from 10 to 90 μm. If the thickness is 1 to 250 μm, it can have practical applications for making a self-supporting film.

In the present invention, a polyimide film having a total light transmittance at a thickness of 80 μm is preferably 85% or more, more preferably 88% or more, and even more preferably 89% or more.
In the present invention, a polyimide film having a yellow index (YI value) of 2.7 or less, more preferably 2.5 or less, and even more preferably 2.2 or less can be produced.
In the present invention, a polyimide film having a glass transition temperature of preferably 220 ° C or higher, more preferably 250 ° C or higher, and even more preferably 280 ° C or higher can be made.
Specifically, the total light transmittance, YI value, and glass transition temperature of the polyimide film can be measured by the method described in the examples.

In the present invention, a polyimide film having a phase retardation value (Rth) in a thickness direction of preferably 200 nm or less, more preferably 150 nm or less, still more preferably 120 nm or less, and still more preferably 90 nm or less can be produced. In addition, in this specification, "low phase retardation" means that the phase retardation value (Rth) in the thickness direction is low, and the phase retardation value (Rth) in the thickness direction should fall within the aforementioned range.
In the present invention, a polyimide film having a birefringence of 0.003 or less, more preferably 0.0025 or less, still more preferably 0.002 or less, and still more preferably 0.0012 or less can be prepared.
In the present invention, the tensile elongation at break (measurement temperature: 23 ° C, humidity: 50% RH) is preferably 8% or more, more preferably 8.2% or more, even more preferably 8.5% or more, and even more preferably 9 % Polyimide film.
Specifically, the phase retardation value (Rth), the birefringence, and the tensile elongation at break of the polyimide film in the thickness direction can be measured by the method described in the examples.

The polyimide film containing the polyimide of the present invention can be suitably used as a film for various members such as color filters, flexible displays, semiconductor parts, and optical members.
[Example]

Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited in any way by these examples.
The physical properties of the polyimide solution and the polyimide film obtained in the following examples and comparative examples were measured by the following methods.
(1) Solid content concentration:
The measurement of the solid content concentration of the polyimide solution (polyimide varnish) was performed by heating the sample in a small electric furnace MMF-1 manufactured by AS ONE Co., Ltd. at 300 ° C for 30 minutes. Calculated from the difference in sample weight.
(2) Film thickness:
The film thickness was measured using a micrometer manufactured by Mitutoyo Co., Ltd.

(3) The total light transmittance and YI value were measured in accordance with JIS K7361-1: 1997 using a color-turbidity simultaneous measuring device "COH400" manufactured by Nippon Denshoku Industries Co., Ltd.
(4) The glass transition temperature was measured using a differential scanning calorimeter device (DSC6200) manufactured by SII NanoTechnology Co., Ltd., and the DSC measurement was performed at a temperature rise rate of 10 ° C / min to determine the glass transition temperature.

(5) Birefringence, Rth
The values of nx, ny, and nz at a measurement wavelength of 590 nm were measured using an ellipsometry "M-220" manufactured by JASCO Corporation. Using this value, the phase retardation value (Rth) in the thickness direction defined by the following formula is obtained, and the birefringence (Δn) is obtained by dividing by the thickness of the film.
Rth = [(nx ＋ ny) / 2-nz] × d
Δn = (nx ＋ ny) / 2-nz
[In the formula, nx represents the largest refractive index among the refractive indexes within the plane of the polyimide film; ny represents the smallest refractive index; nz represents the refractive index in the thickness direction; and d represents the thickness (nm) of the film. ]

(6) The elongation measurement is based on ASTM-882-88 using a tensile tester "STROGRAPH VC-1" manufactured by Toyo Seiki Co., Ltd. to measure the temperature at 23 ° C, humidity at 50% RH, distance between fixtures at 50 mm, and tensile strength. A tensile test was performed under the conditions of an elongation speed of 50 mm / minute, and the elongation at break at break was determined. The higher the elongation at break, the better the extensibility of the film.

<Example 1>
9.96 g (0.028 mole) of 9,9-bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical Industry Co., Ltd.) as a diamine component, 2,2-bis [4- (4-amino group) Phenoxy) phenyl] propane (manufactured by Wakayama Seiki Chemical Industry Co., Ltd.) 8.62 g (0.021 mole) and 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl (Manufactured by Wakayama Seiki Chemical Industry Co., Ltd.) 6.72 g (0.021 mol) and 46.86 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) are put into a stainless steel half-moon shaped stirring blade, a nitrogen introduction tube, A 300 mL 5-necked round-bottom flask with a Dean-Stark device, a thermometer, and a glass end cap was used as a cooling tube, and the solution was obtained by stirring at a temperature of 70 ° C. in a nitrogen environment at a speed of 200 rpm.
As a tetracarboxylic acid component, 16.47 g (0.07 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and γ-butyrolactone (Mitsubishi Chemical Corporation) Co., Ltd.) 11.72 g was added to this solution in one shot, and then 3.54 g of triethylamine (manufactured by Kanto Chemical Co., Ltd.) as a sulfonium imidization catalyst was added and heated with a mantle heater for a period of time. The temperature in the reaction system was raised to 190 ° C in about 20 minutes. The distillate was collected, and the rotation speed was adjusted in accordance with the increase in viscosity, while maintaining the temperature in the reaction system at 190 ° C and refluxing for 5 hours.
Thereafter, 97.62 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) was added, and the temperature in the reaction system was cooled to 120 ° C., followed by stirring for about 3 hours to homogenize the polymer to obtain a solid content concentration of 20% by mass. Hydrazone solution. Then, the obtained polyfluorene imide solution was applied to a glass plate, and the solvent was volatilized by holding the hot plate at 100 ° C. for 60 minutes, thereby obtaining a colorless and transparent primary dry film having self-supporting property. This film was fixed to a stainless steel frame, and heated at 250 ° C. for 2 hours in a hot air dryer to evaporate the solvent to obtain a film having a thickness of 56 μm. The results are shown in Table 1.

<Example 2>
9.96 g (0.028 mole) of 9,9-bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical Industry Co., Ltd.) as a diamine component, 2,2-bis [4- (4-amino group) Phenoxy) phenyl] propane (manufactured by Wakayama Seiki Chemical Industry Co., Ltd.) 14.37 g (0.035 mole) and 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl (Made by Wakayama Seiki Chemical Industry Co., Ltd.) 2.24 g (0.007 mol) and 48.38 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) are put into a stainless steel half-moon shaped stirring blade, a nitrogen introduction tube, and A 300 mL 5-necked round-bottom flask with a Dean-Stark device, a thermometer, and a glass end cap was used as a cooling tube, and the solution was obtained by stirring at a temperature of 70 ° C. in a nitrogen environment at a speed of 200 rpm.
As a tetracarboxylic acid component, 16.47 g (0.07 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and γ-butyrolactone (Mitsubishi Chemical Corporation) Co., Ltd.) 12.09g was added to this solution in one shot, and then 3.54g of triethylamine (manufactured by Kanto Chemical Co., Ltd.) as a sulfonium imidization catalyst was added, and heated in a heating bag, which took about 20 minutes. The temperature in the reaction system was raised to 190 ° C. The distillate was collected, and the rotation speed was adjusted in accordance with the increase in viscosity, while maintaining the temperature in the reaction system at 190 ° C and refluxing for 5 hours.
Thereafter, 100.8 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) was added, and the internal temperature of the reaction system was cooled to 120 ° C., followed by stirring for about 3 hours to homogenize the polymer to obtain a solid content concentration of 20% by mass. Hydrazone solution. Then, the obtained polyfluorene imide solution was applied to a glass plate, and the solvent was volatilized by holding the hot plate at 100 ° C. for 60 minutes, thereby obtaining a colorless and transparent primary dry film having self-supporting property. The film was fixed to a stainless steel frame, and heated at 250 ° C. for 2 hours in a hot-air dryer to evaporate the solvent to obtain a film having a thickness of 89 μm. The results are shown in Table 1.

<Example 3>
Diamine component 9,9-bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical Industry Co., Ltd.) 7.32 g (0.021 mole), 2,2-bis [4- (4-amino group) Phenoxy) phenyl] propane (manufactured by Wakayama Seika Chemical Industry Co., Ltd.) 5.75 g (0.014 moles) and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane (Manufactured by Wakayama Seiki Chemical Industry Co., Ltd.) 18.15 g (0.035 mol) and 54.20 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) are put in a stainless steel half-moon shaped stirring blade, a nitrogen introduction tube, and A 300 mL 5-necked round-bottom flask with a Dean-Stark device, a thermometer, and a glass end cap was used as a cooling tube, and the solution was obtained by stirring at a temperature of 70 ° C. in a nitrogen environment at a speed of 200 rpm.
As a tetracarboxylic acid component, 16.47 g (0.07 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and γ-butyrolactone (Mitsubishi Chemical Corporation) Co., Ltd.) 13.55g was added to this solution in one shot, and then 3.54g of triethylamine (manufactured by Kanto Chemical Co., Ltd.), which is an imidization catalyst, was added, and heated in a heating bag. The temperature in the reaction system was raised to 190 ° C. The distillate was collected, and the rotation speed was adjusted in accordance with the increase in viscosity, while maintaining the temperature in the reaction system at 190 ° C and refluxing for 5 hours.
Thereafter, 112.9 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) was added, and after cooling the internal temperature of the reaction system to 120 ° C., the mixture was stirred for about 3 hours to homogenize to obtain a polymer having a solid concentration of 20% by mass Hydrazone solution. Then, the obtained polyfluorene imide solution was applied to a glass plate, and the solvent was volatilized by holding the hot plate at 100 ° C. for 60 minutes, thereby obtaining a colorless and transparent primary dry film having self-supporting property. This film was fixed to a stainless steel frame, and heated at 250 ° C. for 2 hours in a hot air dryer to evaporate the solvent to obtain a film having a thickness of 62 μm. The results are shown in Table 1.

<Example 4>
As a diamine component, 9.88-bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical Industry Co., Ltd.) 4.88 g (0.014 mole), 2,2-bis [4- (4-amino Phenoxy) phenyl] propane (manufactured by Wakayama Seika Co., Ltd.) 11.49 g (0.028 mole) and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane (Manufactured by Wakayama Seiki Chemical Industry Co., Ltd.) 14.52 g (0.028 mol) and 53.81 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) are put into a stainless steel half-moon shaped stirring blade, a nitrogen introduction pipe, A 300 mL 5-necked round-bottom flask with a Dean-Stark device, a thermometer, and a glass end cap was used as a cooling tube, and the solution was obtained by stirring at a temperature of 70 ° C. in a nitrogen environment at a speed of 200 rpm.
As a tetracarboxylic acid component, 16.47 g (0.07 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and γ-butyrolactone (Mitsubishi Chemical Corporation) Co., Ltd.) 13.45g was added to the solution in one shot, and then 3.54g of triethylamine (manufactured by Kanto Chemical Co., Ltd.) as a sulfonium imidization catalyst was added and heated in a heating bag. The temperature in the reaction system was raised to 190 ° C. The distillate was collected, and the rotation speed was adjusted in accordance with the increase in viscosity, while maintaining the temperature in the reaction system at 190 ° C and refluxing for 5 hours.
Thereafter, 112.1 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) was added, and the temperature in the reaction system was cooled to 120 ° C., followed by stirring for about 3 hours to homogenize the polymer to obtain a solid content concentration of 20% by mass. Hydrazone solution. Then, the obtained polyfluorene imide solution was applied to a glass plate, and the solvent was volatilized by holding the hot plate at 100 ° C. for 60 minutes, thereby obtaining a colorless and transparent primary dry film having self-supporting property. The film was fixed to a stainless steel frame, and heated at 250 ° C. for 2 hours in a hot air dryer to evaporate the solvent to obtain a film having a thickness of 74 μm. The results are shown in Table 1.

<Example 5>
As a diamine component, 9.88-bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical Industry Co., Ltd.) 4.88 g (0.014 mole), 2,2-bis [4- (4-amino Phenoxy) phenyl] propane (manufactured by Wakayama Seika Co., Ltd.) 11.49 g (0.028 mole) and 5 (6) -amino-1,3,3-trimethyl-1- (4- Aminophenyl) indane (manufactured by Japan Pure Chemical Co., Ltd.) 7.46 g (0.028 moles) and γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) 45.34 g are put into a stainless steel half-moon shaped stirring blade , A nitrogen introduction tube, a Dean-Stark device equipped with a cooling tube, a thermometer, and a 300 mL 5-necked round-bottom flask with a glass end cap, and under the conditions of an internal temperature of 70 ° C, a nitrogen environment, and a rotation speed of 200 rpm The solution was obtained by stirring.
As a tetracarboxylic acid component, 16.47 g (0.07 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and γ-butyrolactone (Mitsubishi Chemical Corporation) Co., Ltd.) 11.33 g was added to this solution in one shot, and then 3.54 g of triethylamine (manufactured by Kanto Chemical Co., Ltd.) as a sulfonium imidization catalyst was added, and heated in a heating bag, which took about 20 minutes. The temperature in the reaction system was raised to 190 ° C. The distillate was collected, and the rotation speed was adjusted in accordance with the increase in viscosity, while maintaining the temperature in the reaction system at 190 ° C and refluxing for 5 hours.
Thereafter, 94.45 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) was added, and the temperature in the reaction system was cooled to 120 ° C, followed by stirring for about 3 hours to homogenize the polymer to obtain a polymer having a solid content concentration of 20% by mass. Hydrazone solution. Then, the obtained polyfluorene imide solution was applied to a glass plate, and the solvent was volatilized by holding the hot plate at 100 ° C. for 60 minutes, thereby obtaining a colorless and transparent primary dry film having self-supporting property. This film was fixed to a stainless steel frame, and heated at 250 ° C. for 2 hours in a hot-air dryer to evaporate the solvent to obtain a film having a thickness of 85 μm. The results are shown in Table 1.

〈Comparative example 1〉
9.96 g (0.028 mole) of 9,9-bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical Industry Co., Ltd.) as a diamine component, 2,2-bis [4- (4-amino group) Phenoxy) phenyl] propane (manufactured by Wakayama Seika Co., Ltd.) 2.87 g (0.007 mole) and 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl (Manufactured by Wakayama Seiki Chemical Industry Co., Ltd.) 11.21 g (0.035 mol) and 45.35 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) are put into a stainless steel half-moon shaped stirring blade, a nitrogen introduction tube, A 300 mL 5-necked round-bottom flask with a Dean-Stark device, a thermometer, and a glass end cap was used as a cooling tube, and the solution was obtained by stirring at a temperature of 70 ° C. in a nitrogen environment at a speed of 200 rpm.
As a tetracarboxylic acid component, 16.47 g (0.07 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and γ-butyrolactone (Mitsubishi Chemical Corporation) Co., Ltd.) 11.34g was added to this solution in one shot, and then 3.54g of triethylamine (manufactured by Kanto Chemical Co., Ltd.) as a sulfonium imidization catalyst was added and heated in a heating bag. The temperature in the reaction system was raised to 190 ° C. The distillate was collected, and the rotation speed was adjusted in accordance with the increase in viscosity, while maintaining the temperature in the reaction system at 190 ° C and refluxing for 5 hours.
Thereafter, 94.47 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) was added, and the temperature in the reaction system was cooled to 120 ° C., followed by stirring for about 3 hours to homogenize the polymer to obtain a solid content concentration of 20% by mass. Hydrazone solution. Then, the obtained polyfluorene imide solution was applied to a glass plate, and the solvent was volatilized by holding the hot plate at 100 ° C. for 60 minutes, thereby obtaining a colorless and transparent primary dry film having self-supporting property. This film was fixed to a stainless steel frame, and the solvent was evaporated in a hot air dryer at 250 ° C. for 2 hours to obtain a film having a thickness of 69 μm. The results are shown in Table 1.

[Table 1]

The abbreviations in the table are as follows.
HPMDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride [compound represented by formula (a-1)]
BAFL: 9,9-bis (4-aminophenyl) 茀 [Compound represented by formula (b-1) (R: hydrogen atom)]
BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane [compound represented by formula (b-2)]
HFBAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane [compound represented by formula (b-3)]
TMDA: 5 (6) -amino-1,3,3-trimethyl-1- (4-aminophenyl) dihydroindane [compound represented by formula (b-4)]
TFMB: 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl [compound represented by formula (b-5)]

It can be seen from Table 1 that the polyfluorene imine films of Examples 1 to 5 are excellent in colorless transparency and heat resistance, and are also excellent in low phase retardation and elongation. Therefore, all the above characteristics have achieved a good balance. On the other hand, the polyimide film of Comparative Example 1 has a high phase retardation value (Rth) in the thickness direction and is inferior in extensibility, and a film having low phase retardation and excellent extensibility cannot be obtained.

Claims (9)

A polyfluorene imine having a constitutional unit A derived from a tetracarboxylic acid or a derivative thereof and a constitutional unit B derived from a diamine, and the constitutional unit A includes a constitutional unit (A-1) derived from a compound represented by the following formula (a-1) ), The constituent unit B includes a constituent unit (B-1) derived from a compound represented by the following formula (b-1), a constituent unit (B-2) derived from a compound represented by the following formula (b-2), and The structural unit (B-3) derived from the compound represented by the following formula (b-3), the structural unit (B-4) derived from the compound represented by the following formula (b-4), and the formula (b-5) At least one of the constituent units (B-5) of the compound, the proportion of the constituent unit (B-1) to the constituent unit B is less than 50 mol%, and the constituent unit (B-2) is relative to the constituent unit The proportion of B is 15 mol% or more, and the proportion of the total of the constituent units (B-1) and (B-2) in the constituent unit B is 40 mol% or more; [化 1] [Chemical 2] In formula (b-1), R each independently represents a hydrogen atom, a fluorine atom, or a methyl group. For example, the polyimide of item 1 of the scope of patent application, wherein the proportion of the constituent unit (B-1) to the constituent unit B is 5 to 45 mole%. For example, the polyimide of item 1 or 2 of the scope of patent application, wherein the proportion of the constituent unit (B-2) to the constituent unit B is 15 to 70 mol%. For example, the polyimide of any one of the items 1 to 3 of the patent application scope, wherein the total of the constituent unit (B-3), the constituent unit (B-4), and the constituent unit (B-5) is in constituent unit B The proportion is 5 ~ 60 mol%. For example, the polyimide of item 4 of the scope of patent application, wherein the proportion of the constituent unit (B-3) to the constituent unit B is 10 to 60 mol%. For example, the polyimide of item 4 of the scope of patent application, wherein the proportion of the constituent unit (B-4) to the constituent unit B is 10 to 60 mol%. For example, the polyimide of item 4 of the scope of patent application, wherein the proportion of the constituent unit (B-5) to the constituent unit B is 5 to 40 mole%. A polyimide varnish is obtained by dissolving the polyimide in any one of the scope of patent applications 1 to 7 in an organic solvent. A polyimide film comprising the polyimide according to any one of claims 1 to 7 of the scope of patent application.